THREE-DIMENSIONAL POROUS NiSe2 FOAM-BASED HYBRID CATALYSTS FOR ULTRA-EFFICIENT HYDROGEN EVOLUTION REACTION IN WATER SPLITTING

ABSTRACT

A hybrid three dimensional (3D) hydrogen evolution reaction (HER) catalyst that is formed from a porous Ni foam support, a NiSe2 scaffold positioned on the support; and layered transition metal dichalcogenide (LTMDC) or first-row transition metal dichalcogenide particles positioned on the NiSe2 scaffold. The catalyst provides a low onset potential, large cathode current density, small Tafel slopes, and large exchange current densities, similar in catalytic power to Pt HER catalysts.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims benefit of U.S. provisional patent applicationSer. No. 62/337,730 filed May 17, 2016, and titled “Three-DimensionalPorous NiSe₂ Foam-Based Hybrid Catalysts For Ultra-Efficient HydrogenEvolution Reaction In Water Splitting,” which is hereby incorporatedherein by reference in its entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made with government support under Grant No. FA7000-13-10001 awarded by the United States Defense Threatening ReductionAgency (DTRA). The United States government has certain rights in theinvention.

BACKGROUND Field of the Disclosure

This disclosure generally relates to three-dimensional (3D) porous NiSe₂foam-based hybrid catalysts.

Background of the Technology

With the consumption of fossil fuels and their detrimental impact on theenvironment, methods of generating clean power are required. Hydrogen isan ideal carrier for renewable energy, but H₂ generation is inefficientdue to the lack of robust catalysts that are substantially cheaper thanplatinum (Pt). Therefore, there is a recognized need in the field forrobust and durable earth-abundant, cost-effective catalysts that arehighly desirable for H₂ generation from water splitting via a hydrogenevolution reaction (HER).

BRIEF SUMMARY OF THE DISCLOSURE

Herein disclosed, are highly active and durable earth-abundanttransition metal dichalcogenides-based hybrid catalysts that exhibit HERactivity approaching the performance of-Pt-based catalysts of the priorart, and in some embodiments are also more efficient than those ontransitional parent metal dichalcogenides (such as, but not limited to:MoS₂, WS₂, CoSe₂, etc.). The catalysts described herein are constructedby growing in ternary MoS_(2(1-x))Se_(2x) particles orWS_(2(1-x))Se_(2x) on a 3D self-standing porous NiSe₂ foam, leading toin some embodiments, better catalytic activity than MoS₂, MoSe₂ or NiSe₂alone, as supported by calculations. This disclosure, therefore providesa new pathway to cheap, efficient, and sizable hydrogen-evolvingelectrodes by simultaneously tuning the number of catalytic activesites, porous structures, heteroatom doping and electrical conductivityby growing ternary MoS₂₍₁₋₂₎Se_(2x) or WS_(2(1-x))Se_(2x) particles onporous NiSe₂ foam with excellent catalytic activity comparable toprecious Pt catalysts, suggesting applications in large-scale watersplitting.

The disclosure is further drawn to methods of making suchthree-dimensional (3D) porous NiSe₂ foam-based hybrid catalysts whereinporous NiSe₂ foam is synthesized by direct selenization of commercial Nifoam, first-row transition metal dichalcogenides (TMDC) such as CoS₂,CoSe₂, FeSe₂, FeS₂, NiSe₂, NiS₂, layered TMDC catalysts (MoS₂, WS₂,MoSe₂, etc.) or combinations thereof are then grown on its surface. Thedisclosure is still further drawn to catalysts as described herein,which are constructed in some embodiments by growing ternaryMoS_(2(1-x))Se_(2x) or WS_(2(1-x))Se_(2x) particles on a 3Dself-standing porous NiSe₂ foam.

Herein disclosed are exemplary embodiments of a three dimensional (3D)porous hydrogen evolution reaction (HER) catalyst.

In some embodiments herein disclosed is a three dimensional (3D)hydrogen evolution reaction (HER) catalyst, comprising a porous Ni foamsupport; a NiSe₂ scaffold positioned on the support; and layeredtransition metal dichalcogenide (LTMDC), or first-row TMDC particleswith binary or ternary phase positioned on the NiSe₂ scaffold, in someembodiments of the catalyst the transition metal dichalcogenides (LTMDC)are selected from the group consisting of CoS₂, CoSe₂, FeS₂, FeSe₂,NiSe₂, NiS₂, MoS₂, WS₂, MoSe₂, WSe₂, and a combination of any of theforegoing, in other embodiments the layered transition metaldichalcogenides (LTMDC) particles are MoS_(2(1-x))Se_(2x) orWS_(2(1-x))Se_(2x) particles, in further embodiments the layers ofMoS_(2(1-x))Se_(2x) or WS_(2(1-x))Se_(2x) particles are verticallyoriented layers. In some embodiments a catalyst comprises a NiSe₂scaffold, which further comprises mesoporous pores. In some embodiments,the mesoporous pores are between 0.001 nm and 50 nm in diameter, and inother embodiments, the pores comprise a surface roughness (Ra) ofbetween 0.1 and 50, 1 and 30, and 10 and 20, and 0.1 and 10. In someembodiments herein disclosed the NiSe₂ scaffold comprises active edgesites for HER. In some embodiments herein disclosed the catalyst has atleast one of: a low onset potential, large cathode current density,small Tafel slopes, or large exchange current density.

In some embodiments a low onset or overpotential is between −10 and −200mV, in other embodiments a low onset potential is between about −20 mVand about −145 mV, in further embodiments a low onset potential isbetween −50 and −100 mV. In some further embodiments a low onsetpotential is −20 mV; and in another embodiment the low onset potentialis −145 mV.

In some embodiments a large current density is about −10 mV at 10 mA/cm²to about −120 mV at 10 mA/cm², in other embodiments a large currentdensity is about −50 mV at 10 mA/cm² to about −100 mV at 10 mA/cm², andin further embodiments a large current density is about −70 mV at 10mA/cm² to about −100 mV at 10 mA/cm², in a further embodiment a largecurrent density is about −69 mV at 10 mA/cm², and in a still furtherembodiment a large current density is about −88 mV at 10 mA/cm². In someembodiments the current density may be a cathode current density.

In some embodiments a low Tafel slope is about 10 mV/dec to about 100mV/dec, in other embodiments a low Tafel slope is about 20 mV/dec toabout 80 mV/dec, and in further embodiments a low Tafel slope is about40 to about 60 mV/dec, in another further embodiment, a low Tafel slopeis about 43 mV/dec, and in a still further embodiment a low Tafel slopeis about 46.7 mA/dec.

In some embodiments a large exchange current density is about 10 toabout 1000 μA/cm², in other embodiments a large exchange current densityis about 100 to about 600 μA/cm², and in another embodiment a largeexchange current density is about 200 to about 600 μA/cm², in a furtherembodiment a large exchange current density is about 495 μAcm², and in astill further embodiment a large exchange current density is about 214.7μA/cm². μA/cm2

In other embodiments a method of making a three dimensional hydrogenevolution reaction (HER) catalyst is disclosed, comprising: positioninga porous Ni foam support, selenizating the Ni foam support, and forminga NiSe₂ scaffold; and growing a layered transition metal dichalcogenides(LTMDC) particles on the NiSe₂ scaffold, to form a three dimensionalhydrogen evolution reaction (HER) catalyst. In some embodimentsselenizating is in an Ar atmosphere, in other embodiments selenizatingis at 450° C.—600° C. In some embodiments of the method hereindisclosed, the NiSe₂ scaffold is HER active, and the grown layeredtransition metal dichalcogenides comprises a large number of exposedactive edge sites. In other embodiments the layered transition metaldichalcogenide particles are of MoS_(2(1-x))Se_(2x) particles. In otherembodiments the layered transition metal dichalcogenide particles are ofMoS₂, MoSe₂, WS₂, WSe₂ or WS_(2(1-x))Se_(2x). In some embodiments hereindisclosed growing of the MoS_(2(1-x))Se_(2x) particles orWS_(2(1-x))Se_(2x) particles are in a vertical layer orientation fromthe NiSe₂ scaffold, In some embodiments herein disclosed growing of theWS_(2(1-x))Se_(2x) particles are in an edge-orientation from the NiSe₂scaffold. In some embodiments, one layer of MoS_(2(1-x))Se_(2x)particles or WS_(2(1-x))Se_(2x) particles is about 0.1 to 75 nm inthickness. In other embodiments herein disclosed, one layer ofMoS_(2(1-x))Se_(2x) particles or WS_(2(1-x))Se_(2x) particles is about0.62 nm in thickness. In some embodiments the surface is grown atbetween 450° C. and 600° C., and in other embodiments, the layer ofMoS_(2(1-x))Se_(2x) particles or WS_(2(1-x))Se_(2x) particles is grownat 500° C. degrees. In some embodiments herein disclosed the catalystcomprises a large 3-D porous surface area.

In some embodiments herein disclosed is an electrode, comprising: athree dimensional Hydrogen Evolution Reaction (HER) catalyst, whereinthe electrode comprises, a porous NiSe₂ foam support, and layeredtransition metal dichalcogenides (LTMDC) particles, or first-rowtransition metal dichalcogenides positioned on the NiSe₂ scaffold, andwherein the catalyst has at least one of: an low onset potential, largecathode current density, small Tafel slopes and large exchange currentdensity.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 depicts a schematic diagram, and the morphologies of as-grownporous NiSe₂ foam and ternary MoS_(2(1-x))Se_(2x) particles synthesizedon the porous NiSe₂ foam. (FIG. 1A)=The procedures for growingMoS_(2(1-x))Se_(2x) particles on porous NiSe₂ foam. (FIG. 1B)=Typicallow (left) and high (right)-magnification SEM images showing the surfaceroughness of the NiSe₂ foam grown at 600 ° C. from commercial Ni foam.(FIG. 1C)=Low (left) and high (right)-magnification SEM images showingthe morphologies of ternary MoS_(2(1-x))Se_(2x) particles distributed onporous NiSe₂ foam grown at 500° C.

FIG. 2. shows characterization of the ternary MoS_(2(1-x))Se_(2x)/NiSe₂foam hybrid catalysts by high-resolution TEM, XPS and Raman. (FIG. 2A,and FIG. 2B)=TEM images showing the vertical layer orientation ofMoS_(2(1-x))Se_(2x) particles grown on different regions of porous NiSe₂foam. Scale bar: 5 nm. (FIG. 2C-FIG. 2E)=Detailed XPS analysis of the Mo3d, S 2p and Se 3d spectra in different samples, such as binary MoS₂particles on Si, MoS_(2(1-x))Se_(2x) particles on Si andMoS_(2(1-x))Se_(2x) particles on porous NiSe₂ foam. (FIG. 2F)=Ramanspectra measured on different samples.

FIG. 3. Shows the electro-catalytic performance of different catalystsfor hydrogen evolution. (FIG. 3A)=The polarization curves recorded onas-obtained MoS_(2(1-x))Se_(2x)/NiSe₂ foam hybrid, binary MoS₂/NiSe₂foam hybrid and pure NiSe₂ foam electrodes compared to a Pt wire. (FIG.3B)=Tafel plots of the polarization curves recorded on the catalystspresented in FIG. 3A. (FIG. 3C)=Polarization curves showing negligiblecurrent density loss of ternary MoS_(2(1-x))Se_(2x)/NiSe₂ hybridelectrodes initially and after 1000 CV cycles. (FIG. 3D)=Time dependenceof current density recorded on the MoS_(2(1-x))Se_(2x)/NiSe₂ hybridelectrode under a given potential—121 mV. (FIG. 3E)=Plot showing theextraction of the double-layer capacitance (C_(dl),) from differentelectrodes. (FIG. 3F)=Electrochemical impedance spectroscopy (EIS)Nyquist plots of the MoS_(2(1-x))Se_(2x)/NiSe₂ hybrid electrode incomparison with binary MoS₂/NiSe₂ hybrid and pure NiSe₂ foam electrodes.The data were fit to the simplified Randles equivalent circuit shown inthe inset.

FIG. 4. Shows density functional theory calculations. (FIG.4A)=Calculated adsorption free energy diagram for hydrogen (H*)adsorption at the equilibrium potential for MoSSe/NiSe₂ hybrid, binaryMoS₂ and MoSSe catalysts. (FIG. 4B)=Intermediate structures of hydrogenbound MoSSe/MoSSe, MoSSe/NiSe₂(100), MoSSe/NiSe₂(110) and MoSSe/NiSe₂(111).

FIG. 5 shows that comparing the relative peak intensity between 250 cm⁻¹and 380 cm⁻¹, the estimated atomic ratio between S and Se is about 1.

FIG. 6 shows Xray Powder Defraction Analysis of embodiments of thecatalysts herein described.

FIG. 7 shows electrochemical double-layer capacitances (C_(dl)) forevaluation of the electrochemically effective surface areas of catalystsherein disclosed.

FIG. 8 shows a schematic diagram (a) and detailed morphologies (b-e) ofedge-oriented WS_(2(1-x))Se_(2x) particles supported on 3D porous NiSe₂foam. Low (b) and high (c) magnification SEM morphologies ofWS_(2(1-x))Se_(2x) particles grown at 500° C. on 3D porous NiSe₂ foam.(d,e) Typical HRTEM images showing a large number of exposed edge sitesin WS_(2(1-x))Se_(2x) particles grown on 3D porous NiSe₂ foam.

FIG. 9. Shows chemical composition analysis of the hybrid catalyst byXPS and Raman spectroscopy. (a) W 4f, (b) S 2p, and (c) Se 3d XPSspectra of the WS_(2(1-x))Se_(2x)-based materials. (d) Raman spectra ofthe WS₂ or WS_(2(1-x))Se_(2x) particles on different substrates.

FIG. 10. Shows electrochemical performance of as-prepared hybridelectro-catalysts in comparison with a Pt wire and pure NiSe₂ support.(a) The polarization curves recorded on different catalysts: pure NiSe₂foam, WS₂ on porous NiSe₂ foam, WS_(2(1-x))Se_(2x) on porous NiSe₂ foamand a Pt wire. (b) The corresponding Tafel plots extracted from thecurves shown in panel a. (c) Polarization curves ofWS_(2(1-x))Se_(2x)/NiSe₂ catalyst initially and after 1000 CV scans. (d)Time dependence of current density of the hybrid catalyst under a staticoverpotential of −145 mV.

FIG. 11. Shows double-layer capacitance (C_(dl)) measurements andNyquist plots by EIS. (a) Electrochemical cyclic voltammogram ofWS₂/NiSe₂ hybrid catalyst at different scan rates from 2 to 20 mV/s withan interval point of 2 mV/s. (b) Electrochemical cyclic voltammogram ofWS_(2(1-x))Se_(2x)/NiSe₂ hybrid catalysts with the scan rates rangingfrom 2 to 18 mV/s with an interval point of 2 mV/s. (c) Linear fittingof the capacitive currents of the catalysts vs the scan rates. (d)Nyquist plots showing the facile electrode kinetics of the hybridcatalysts WS₂/NiSe₂ and WS_(2(1-x))Se_(2x)/NiSe₂.

DETAILED DESCRIPTION OF THE DISCLOSED EXEMPLARY EMBODIMENTS

Three-dimensional porous NiSe₂ foam was directly synthesized by directthermal selenization of commercial Ni foam. Then first-row transitionmetal dichalcogenides (TMDC) such as CoS₂, CoSe₂, FeSe₂, FeS₂, NiSe₂,NiS₂ or, layered TMDC catalysts (MoS₂, WS₂, MoSe₂, etc.) or the mixedcompounds (Ni_(1-x)Co_(x)S₂, Co_(1-x)Mo_(x)S₂, etc.) were grown on itssurface. Due to the three-dimensional nature, good electricalconductivity, and mesoporous structures with rough surface, the 3D NiSe₂foam is a suitable conductive scaffold to support other HER-activecatalysts. The resulting hybrid catalysts exhibit the desired catalyticperformance in the HER, demonstrating low onset potential, large cathodecathodic current density, small Tafel slopes and large exchange currentdensity. Most of the catalysts outperform the state-of-the-art catalystsand exhibit catalytic performance close to the performance of Ptcatalysts. Considering the low cost and earth abundance of thesecompounds, they are alternatives to Pt potentially used in watersplitting. In particular, the starting material Ni foam is commerciallyavailable, in large scale, and inexpensive so the as-obtained hybridcatalysts can be used as sizable hydrogen evolving electrodes. Further,HER-active porous NiSe₂ foam has been directly synthesized fromcommercial Ni foam, and then utilized as the conductive scaffold forsupporting other HER-active catalysts. The resulting hybrid catalystsexhibit improved catalytic performance, compared to the catalysts of theprior art based on layered transition metal dichalcogenides (MoS₂, WS₂,etc.) and first-row transition metal dichalcogenides (CoS₂, CoSe₂,NiSe₂, etc.) See for example: Zhou H. et al., Nano Energy (2016) 20,29-36, which is incorporated herein in its entirety by reference.

Hydrogen (H₂) is a promising energy carrier because of its high energydensity and no pollution gas emission. One direct and effective route togenerate H₂ is based on electro-catalytic hydrogen evolution reaction(HER) from water splitting, in which an efficient catalyst is requiredto ensure the energy efficiency. Pt-based noble metals are the mostactive catalysts, but they are not suitable for large-scale applicationsbecause of their high costs and scarcity on earth. Thus, someembodiments disclosed herein are drawn to electro-catalysts based onearth-abundant and cost-effective materials and further embodiments aredrawn to methods of fabricating electro-catalysts based onearth-abundant and cost-effective materials.

However, most of the Earth-abundant transition metal compounds, such asmetal sulfides, selenides, phosphides, carbides, and their compositesexhibit inferior catalytic efficiency to Pt, and many involvecomplicated preparation methods and multiple steps that increase thecosts. Progress has been obtained for HER based on layered transitionmetal dichalcogenides (LTMDs) such as MoS₂ either in the form ofcrystalline or amorphous states, and in molecular mimics, but theseprior art catalysts are still inferior to Pt resulting from the lowdensity and reactivity of active sites, poor electrical transport, andinefficient electrical contact to the electrode.

Further, the prior art discloses that carbon-based materials aregenerally used as the catalyst support for layered transition metaldichalcogenides (LTMDs, MoS₂, WS₂, etc.) by virtue of their high surfacearea and good conductivity. The catalytic HER performance of suchcarbon-supported layered transition metal dichalcogenides is greatlyimproved, however complex synthesis procedures are required, which leadto increased costs. Double-gyroid structures are also disclosed in theprior art for MoS₂ catalyst, and comprise numerous nanopores withexposed edge sites, which are the catalytic active sites rather than thebasal planes, but the development bottleneck of the double-gyroidstructures is that the catalyst itself has intrinsically poorconductivity. Thus, even though MoS₂ has been established as aneffective HER catalyst, it has previously been difficult to obtainsatisfactory catalysts at low cost on par with the current Pt catalysts.

The majority of HER catalysts of the prior art are based onnanostructures (nanoparticles, nanosheets, etc.) making it necessary touse binder polymers (for example, nafion solution) in order to fastenthe catalysts onto conducting substrates, such as glassy carbonelectrodes, which increases the cost. This problem can be solved bygrowing the active catalysts directly onto self-standing conductingskeletons as the current collectors. Therefore, in some embodiments, acatalyst grown on three-dimensional supports with multiple roughsurfaces, lots of porous structures and good conductivity is disclosed.Considering the high cost for material synthesis, use of graphene orcarbon nanotube is not feasible. Instead, Ni foam is a good startingmaterial because of its low price, commercial availability, andthree-dimensional skeleton structure (FIG. 1a ). Ni foam is not stablein acid electrolytes because of corrosion. However, direct selenizationof Ni foam into porous NiSe₂ foam in Ar atmosphere converts Ni foam toporous stable NiSe₂ foam (FIG. 1b ) that is HER active and stable inacid. Numerous additional mesoporous pores are generated in the NiSe₂regions leading to a rough surface, which provide preferential sites forgrowing LTMD catalysts with vertically oriented layers. Thus, manyactive edge sites may be introduced by growing LTMD catalysts on 3Dporous NiSe₂ foam.

Therefore, disclosed herein in some embodiments, are three-dimensionalhybrid catalysts on mesoporous supports which comprise a high surfacearea for catalyst loading, fast proton transfer and greater contactareas with reactants during the catalytic process. Embodiments disclosedherein are configured to improve the distribution and electricalconductivity of such catalysts on the supports and expose a large numberof active edge sites. Furthermore, in some embodiments, arranging twodifferent materials such as growing ternary MoS_(2(1-x))Se_(2x)particles with vertically aligned layers on a three-dimensional porousHER-active conductive NiSe₂ scaffold, has the ability to take advantageof the merits of carbon materials (high surface area and good electricalconductivity), double-gyroid structures (three-dimensional, porous andmany exposed edge sites) and synergistic effects between two differentcatalysts. In some embodiments, such hybrid catalysts display a highlyefficient HER performance that approaches the levels of Pt catalysts;and display a catalytic performance superior to that reported onwell-studied transitional parent metal dichalcogenides (MoS₂, WS₂,CoSe₂, NiSe₂). In some embodiments disclosed herein, 3D porous NiSe₂foam is configured as a conductive skeleton to load ternaryMoS_(2(1-x))Se_(2x) catalysts, thereby utilizing the electricalconductivity, porous structures, and high surface area of the NiSe₂foam. Scanning electron microscopy (SEM; FIG. 1C) images clearly showthat small ternary particles are uniformly distributed on the porousNiSe₂ foam, indicating that the surface of NiSe₂ foam is suitable fordispersing the particles, which is important for the electro-catalyticperformance of LMDT catalysts.

EXAMPLES Example 1

The chemical composition of the as-grown MoS_(2(1-x))Se_(2x) particleswere examined by high-resolution transmission electron microscopy (TEM),X-ray photoelectron microscopy (XPS), Raman spectroscopy, and energydispersive X-ray spectroscopy (EDS). According to the TEMcharacterizations (FIG. 2a,b ), it is obvious that the layers of ternaryMoS_(2(1-x))Se_(2x) particles grow with vertical orientation on a largedensity on NiSe₂ surface, suggesting that a large number of active edgesites are exposed at the surface of MoS_(2(1-x))Se_(2x) particles. Thisis reasonable since the surface of NiSe₂ foam is rough and curved, whichis favorable for the growth of layered materials with vertically alignedlayers.

XPS spectra in the hybrid reveal the presence of Ni, Mo, S, and Seelements (FIGS. 2c-e ). However, due to the presence of Se elements inporous NiSe₂ foam with an oxidation state similar toMoS_(2(1-x))Se_(2x), it is difficult to demonstrate the selenization ofMoS₂ after its growth on NiSe₂foam. Instead, to confirm the chemicalcomposition of the molybdenum compound, a precursor-decorated Sisubstrate is placed under the NiSe₂ foam during the second selenization.It is clear that the (NH₄)₂MoS₄ precursor has been converted to adistinctive ternary alloy phase at 500° C. from the prominent Mo, S andSe signals in the XPS spectra (FIGS. 2c-e ). Especially in the Ramanspectra (FIG. 2f ), in comparison with pure MoS₂ that two prominentRaman peaks are located at 380 cm ⁻¹ (E_(1g)) and 406 cm⁻¹ (A_(2g)),there is another obvious Raman peak located at 250 cm⁻¹ for the sampleswith a ternary phase, which can be ascribed to the E_(2g) mode of Mo—Sebond. Compared to Raman mode of bulk MoSe₂ crystals (˜242 cm⁻¹), theblue shifts of this peak to 250 cm⁻¹ indicate a ternary a MoS_(2(1-x)),Se_(2x) compound rather than a mixture of two solid phases. This Ramanfeature is also found when the ternary phase is grown on porous NiSe₂foam, which is consistent with previously reported results on ternaryMoS_(2(1-x))Se_(2x) single crystals. By comparing the relative peakintensity between 250 cm ⁻¹ and 380 cm⁻¹, wherein the estimated theatomic ratio between S and Se to be around 1, which is further supportedby the EDS analysis (FIG. 5).

To evaluate the catalytic performance of these ternary MoS, it wasestimated that the atomic ratio between S and Se to be around 1, whichis further supported by the EDS analysis (FIG. 6) To evaluate thecatalytic performance of the ternary MoS_(2(1-x))Se_(2x) particles grownon 3D porous NiSe₂ foam, electro-catalytic measurements were performedvia a standard three-electrode setup in a 0.5M H₂SO₄ electrolytede-aerated with high-purity N₂ were performed. The loading ofMoS_(2(1-x))Se_(2x) catalysts is around 4.5 mg/cm², and FIG. 3a showsthat the self-standing porous hybrid catalyst can afford geometriccurrent densities of about 10 mA/cm² at a low overpotential 69 mV forthe ternary MoS_(2(1-x))Se_(2x) hybrid electrode. In contrast, forbinary MoS₂ on NiSe₂ foam and pure NiSe₂ foam, overpotentials of 116 mVand 192 mV respectively are needed to achieve about 10 mA/cm². Thecatalytic overpotential (69 mV) of the MoS_(2(1-x))Se_(2x)/NiSe₂ hybridis also much lower than those of the best catalysts thus far based onLTMDs MoS₂ (−110 mV), WS₂ (−142 mV) and WS_(2(1-x))Se_(2x) (−170 mV),and first-row transition metal dichalcogenides CoSe₂ (−139 mV), NiSe₂(−136 mV) and CoS₂ (−142 mV). This suggests that the ternaryMoS_(2(1-x))Se_(2x) particles/NiSe₂ foam hybrid is a highly functionalHER catalyst. Further, a Tafel slope, which is an inherent property ofthe catalyst, can be obtained by extracting the slopes from the linearregions in Tafel plots (FIG. 3b ). It is found that the ternaryelectrode possesses a smaller Tafel slope (43 mV/dec) than that ofbinary MoS₂ on NiSe₂ foam (67 mV/dec) and pure NiSe₂ foam (49 mV/dec).In addition, the hybrid catalyst disclosed herein leads to a Tafel slopemuch lower than many previously reported cheap and efficient HERcatalysts in the same electrolyte. Further, based on the intercept ofthe linear region of the Tafel plots, the exchange current densities(j_(0,geometrical)) at the thermodynamic redox potential (η=0) can becalculated to be 495 μAcm⁻² for the ternary-phase hybrid catalysts withNiSe₂ foam. This exchange current density is one to two orders ofmagnitude larger than those of layered transition metal dichalcogenidesMoS₂ and WS₂, or first-row transition metal dichalcogenides CoSe₂ andCoS₂ catalysts of the prior art. It is well known that it is difficultto prepare a self-standing catalyst simultaneously possessing low onsetoverpotential, large current density, small Tafel slope and largeexchange current density. Thus, considering the small onsetoverpotential (˜20 mV), large current density (−69 mV at 10 mA/cm²), lowTafel slopes (˜43 mV/dec) and large exchange current density (˜495μAcm⁻²), embodiments of the catalyst disclosed herein comprise catalyticfunction at a level displayed by Pt catalysts of the prior art, and arealso catalytically higher functioning than most MoS₂-based catalysts.

Aside from a stringent requirement for high HER activity, stability isanother important criterion in evaluating the catalytic performance ofan electro-catalyst. In embodiments disclosed herein, a long-term cyclicvoltammetry test between −0.20 and 0.07 V vs RHE shows no significantdegradation of cathodic current densities for the catalyst before, andafter 1000 cycles (FIG. 3c ). In other embodiments, the cathodic currentdensity for the hybrid catalyst remains stable, and exhibits no obviousdegradation for electrolysis at a given potential over a long period(FIG. 3d ), suggesting the potential use of this catalyst over a longtime in an electrochemical process. In some embodiments, after long-termstability and cyclability tests, the catalytic performance of the hybridcatalyst disclosed herein still shows no degradation (FIG. 3c ).

To elucidate the origin of the differences in the overall catalyticperformance among different catalysts, a simple cyclic voltammetry (CV)method was utilized in some embodiments to measure the correspondingelectrochemical double-layer capacitances (C_(dl)), and thereforeallowing evaluation of the electrochemically effective surface areas(FIG. 7). Taking consideration of the direct proportion between theeffective surface area and double-layer capacitance, capacitance valuesC_(dl) may be directly compared. By plotting the positive and negativecurrent density differences (Δj=j_(a)-j_(c)) at a given potential (0.15V vs. RHE) against the CV scan rates, the double-layer capacitances(C_(dl),), which is equal to half the value of the linear slopes of thefitted lines in the plots, can be calculated. As shown in FIG. 3e , theMoS_(2(1-x))Se_(2x)/NiSe₂ hybrid electrode exhibits a C_(dl) value of319.15 mF/cm², which is one order of magnitude larger than that of pureMoS₂/NiSe₂ foam (30.88 mF/cm²) and about 40 times larger than that ofpure NiSe₂ foam (7.48 mF/cm²), demonstrating the proliferation of activesites in the porous hybrid catalyst, which accordingly results in theimproved catalytic performance. In some embodiments, electrochemicalimpedance spectroscopy (EIS) was carried out to examine the electrodekinetics under the catalytic HER operating conditions (FIG. 3f ).According to the Nyquist plots and data fitting to a simplified Randlescircuit, the results disclosed herein clearly reveal that thecharge-transfer resistance (R_(ct)˜0.5 Ω) for theMoS_(2(1-x))Se_(2x)/NiSe₂ hybrid is smaller than that for pureMoS₂/NiSe₂ (R_(ct)˜8 Ω) or for porous NiSe₂ foam alone (R_(ct)˜22 Ω),which may be due to the chemical bonding between MoS_(2(1-x))Se_(2x) andNiSe₂ foam in contrast to the physisorption of MoS₂ particles on solidNiSe₂. This was confirmed by the quantum mechanics (QM) calculations asdescribed below. Additionally, all the catalysts have very small seriesresistances (R_(s)˜0.6-1.2 Ω), indicative of high-quality electricalintegration of the catalyst with the electrode. Therefore, to understandthe improvement on the catalytic hydrogen evolution of theMoS_(2(1-x))Se_(2x)/NiSe₂ hybrid catalysts, QM calculations at thedensity functional theory (DFT) level (PBE flavor) were performed tocalculate the binding free energies of hydrogen on the Mo atom.

To further analyze the improvement on the catalytic hydrogen evolutionof the MoS_(2(1-x))Se_(2x)/NiSe₂ hybrid catalysts, QM calculations atthe density functional theory (DFT) level (PBE flavor) were performed tocalculate the binding free energies of hydrogen on the Mo atom (See forexample: Zhou H. et al., Efficient hydrogen evolution by ternarymolybdenum sulfoselenide particles on self-standing porous nickeldiselenide foam, Nature Comms. 2016, 7, 12765 (doi:10.1038/ncomms12765);and Zhou, H., et al, Outstanding Hydrogen evolution reaction in watersplitting catalyzed by porous nickel diselenide electro-catalysts likePt, Energy and Environ Sci., 2016, 00, 1-3; each of which isincorporated herein in its entirety by reference). Although it wasoriginally assumed that the edge S atom is the catalytic atom inhydrogen evolution on MoS₂ embodiments herein it is found that H₂formation proceeds through the Mo atom via the Heyrovsky reaction andhas a lower barrier than the Heyrovsky and Volmer reaction on the Satom. Therefore, a lower hydrogen binding energy on the Mo atom was usedas the indicator for lower barrier in the Heyrovsky step. Since thereare various exposed facets in the as-prepared NiSe₂ foam (FIG. 6), thereaction was in some embodiments modeled on the simple low-index (100),(110) and (111) surfaces of NiSe₂. As shown in FIG. 4a , ΔG_(H*) is 8.4kcal/mol for hydrogen adsorbed onMoS_(2(1-x))Se_(2x)/MoS_(2(1-x))Se_(2x), which is more reactive thanMoS₂/MoS₂ with a ΔG_(H*) of 10.6 kcal/mol, agreeing with the reportedexperimental result. In contrast, once the MoS_(2(1-x))Se_(2x) particlesare hybridized with NiSe₂ foam, the relevant ΔG_(H*) onMoS_(2(1-x))Se_(2x)/NiSe₂(100) and MoS_(2(1-x))Se_(2x)/NiSe₂(110) arefurther decreased to 2.7 kcal/mol and 2.1 kcal/mol, respectively, makingthese hybrid catalysts more active than MoS₂/MoS₂ andMoS_(2(1-x))Se_(2x)/MoS_(2(1x))Se_(2x) in the HER process. To understandthe reason for the improved reactivity of MoS_(2(1-x))Se_(2x)/NiSe₂hybrid catalysts, intermediate structures (FIG. 4b ) were furtherexamined. MoS_(2(1-x))Se_(2x) in some embodiments is found to bechemically bonded to the NiSe₂ substrate on the (100) and (110)surfaces, allowing the electrons to delocalize into the substrate, thuslowering the binding energies of hydrogen and ensuring quick chargetransfer in the HER process as confirmed in the EIS spectra. Thus, DFTcalculations corroborate that the MoS_(2(1-x))Se_(2x)/NiSe₂ hybrid is aneffective electro-catalyst (FIG. 4).

Thus, disclosed herein in some embodiments, are robust and stablehydrogen evolving catalysts, wherein such catalysts are synthesized bygrowing ternary MoS_(2(1-x))Se_(2x) particles on a 3D porous andmetallic NiSe₂ foam. In some embodiments, experimental and theoreticalresults show that these MoS_(2(1-x))Se_(2x)NiSe₂ hybrid catalystsexhibit catalytic performance in the order of the LTMD catalysts (suchas MoS₂, WS₂) and first-row transition metal pyrites (CoSe₂, CoS₂,NiSe₂, etc.) of the prior art. In some embodiments, the catalystsdisclosed herein are effective in catalyzing hydrogen production byintegrating metal dichalcogenides and pyrites into three-dimensionalhybrid architectures that possess high surface area, mesoporousstructures, good electrical conductivity, and abundant active edgesites, making effective such catalysts effective and efficient forlarge-scale water splitting.

Example 2

A further embodiment comprises an efficient and durable hybrid catalystcomposed of tungsten sulfoselenide WS_(2(1-x))Se_(2x)/NiSe₂ particlessupported by 3D porous NiSe₂ foam which was formulated from commercialNi foam via thermal selenization (see for example: Zhou H. et al.,Highly Efficient Hydrogen Evolution from Edge-OrientedWS_(2(1-x))Se_(2x)/NiSe₂, Nano Lett., 2016, 16 (12), pp 7604-7609,incorporated herein in its entirety by reference). Particles disperseuniformly on a NiSe₂ surface with a large number of exposed edge sites.Therefore in some embodiments WS_(2(1-x))Se_(2x)/NiSe₂/NiSe₂ hybrid foamcan be directly employed as a 3D self-standing hydrogen-evolvingelectrode. In some embodiments an electrode as disclosed herein exhibitsan effective HER performance and produces a large current density (inthe order of about −10 mA/cm² at only −88 mV), a low Tafel slope (in theorder of about 46.7 mV/dec), large exchange current density (in theorder of about 214.7 μA/cm²), and is electrochemical stabile.

In some embodiments the catalytic properties are superior to manycatalysts of the prior art, which may in part be attributed to thesynergistic effects of good conductivity and high surface area of porousNiSe₂ foam, and a large number of active edge sites from ternaryWS_(2(1-x))Se_(2x)/NiSe₂ particles.

In some embodiments, the synthesis of the catalyst commences with thegrowth of porous NiSe₂ foam from commercially available Ni foam bydirect selenization (FIG. 8). In some embodiments the original Ni foamis composed of Ni grains that are micrometer in size. After thermalconversion of Ni foam into metallic NiSe₂ foam, additional porousstructures with rough surface are generated, and in some embodimentsmost of metallic Ni is converted to pyrite NiSe₂ as confirmed by powderX-ray diffraction pattern, wherein the remaining small amount ofmetallic Ni contributes to the total conductivity of porous NiSe₂samples. The as-grown NiSe₂ samples were in some embodiments modifiedwith a (NH₄)₂WS₄ precursor, followed by a second selenization at 500° C.in a tube furnace. The SEM images (FIG. 8b,c ) show that theWS_(2(1-x))Se_(2x)/NiSe₂ particles are uniformly dispersed on a porousNiSe₂ foam, which plays a significant role in the catalytic performancebecause of the increased active sites. High-resolution transmissionelectron microscopy (HRTEM), indicate that in some embodiments thelayers of WS_(2(1-x))Se_(2x)/NiSe₂ particles are exposed on the surfaceof NiSe₂ foam (FIG. 8d and e ), which may be attributed to the rough andcurved surface of NiSe₂ foam that is used for layer orientation ofWS_(2(1-x))Se_(2x)/NiSe₂ particles. These exposed layers ofWS_(2(1-x))Se_(2x)/NiSe₂ particles then provide a large number of activeedge sites for the HER. Considering the metallic feature and porousstructures of NiSe₂ foam and that each layer of WS_(2(1-x))Se_(2x)/NiSe₂particles is in some embodiments in direct contact with the NiSe₂ foam,the electrical contact between the WS_(2(1-x))Se_(2x)/NiSe₂ catalyst andthe electrode is increased, which ensures quick electron transfer fromthe electrode to the WS_(2(1-x))Se_(2x)/NiSe₂ particles.

Moreover, in some embodiments, the many porous structures provided byNiSe₂ foam quicken the proton transfer from the electrolyte to thecatalyst surface because of high surface area. Thus, in some embodimentsthe hybrid catalysts simultaneously possess good electrical contact,high-density active edge sites, and 3D porous structures with highsurface area, all of which contribute greatly to the electro-catalytichydrogen evolution. X-ray photoelectron spectroscopy (XPS) and Ramanspectroscopy were utilized to further characterize the chemicalcomposition of the as-prepared catalysts.

In some embodiments, XPS spectra collected onWS_(2(1-x))Se_(2x)/NiSe₂/NiSe₂ hybrid material, detected each of Ni, W,S, and Se elements (FIG. 9a-c ]. The origin of Se (i.e. whether thesignal originates from the WS_(2(1-x))Se_(2x)/NiSe₂ particles or NiSe₂foam) was clarified by performing a selenization at 500° C., and bygrowing the tungsten compound on a Si substrate to clearly detect thepresence of W, S, and Se elements in the relevant XPS data (FIG. 9a-c ).In further embodiments it is possible to detect theWS_(2(1-x))Se_(2x)/NiSe₂ particles on a porous NiSe₂ foam by Ramanspectroscopy because of different vibration modes between NiSe₂ andWS_(2(1-x))Se_(2x)/NiSe₂. As shown in FIG. 9d , for pure NiSe₂ foam,there are four vibration peaks ascribed to the Tg (153.6 cm−1), Eg(172.2 cm ⁻¹), Ag (217.7 cm⁻¹), and Tg (243.7 cm⁻¹) modes of NiSe₂ whilefor pure WS₂, two prominent Raman peaks are detected at 357.5 and 421.0cm⁻¹, which can be attributed to the E¹ _(2g) and A_(1g) modes,respectively. Compared to pure WS₂/NiSe₂ foam, there is another broadpeak appearing at around 257 cm⁻¹ for WS_(2(1-x))Se_(2x)/NiSe₂, whichcan be clearly found on the Raman spectra ofWS_(2(1-x))Se_(2x)/NiSe₂/NiSe₂, and is associated with the correspondingWSe₂-like E¹ _(2g)/2LA features. These observations in Raman and XPSdata confirm the formation of ternary WS_(2(1-x))Se_(2x)/NiSe₂ particleson porous NiSe₂ foam, as compared to bench mark data. In someembodiments and based on Raman spectra, the factor x showing the atomicratio between S and Se is around 0.3, which is further demonstrated bythe X-ray energy dispersive spectroscopy measurement.

In some embodiments, the electro-catalytic hydrogen evolution of thehybrid catalysts, were analyzed by performing electrochemicalmeasurements in a three-electrode configuration in a N₂-saturated 0.5 MH₂SO₄ electrolyte. The loading of WS₂ or WS_(2(1-x))Se_(2x)/NiSe₂particles on porous NiSe₂ foam is at about 5.4 mg/cm². All of thepotentials reported here are referenced to the reversible hydrogenelectrode (RHE).

FIG. 10a shows the polarization curves recorded on the as-preparedhybrid catalysts. For comparison, curves collected on binaryWS_(2(1-x))Se_(2x)/NiSe₂, pure NiSe₂ foam, and a Pt wire are shown,wherein in some embodiments the WS_(2(1-x))Se_(2x)/NiSe₂ hybrid catalystcan provide a geometric current density of −10 mA/cm² at only −88 mV,which is much lower than −108 mV for WS₂/NiSe₂ and −154 mV for pureNiSe₂ foam. This performance outperforms many reported catalysts in theprior art illustrating the effective catalytic performance of ternaryWS_(2(1-x))Se_(2x)/NiSe₂ particles/NiSe₂ foam hybrids reported here forthe HER. In addition, the Tafel slope of theWS_(2(1-x))Se_(2x)/NiSe₂/NiSe₂ hybrid is only 46.7 mV/dec (FIG. 10b ).The exchange current density (j₀) is calculated to be around 214.7μA/cm², larger than most of the values reported on the well-known MoS₂,WS₂, and CoSe₂ catalysts. This, in some embodiments, may be due to theincreased active edge sites from WS_(2(1-x))Se_(2x)/NiSe₂ particlesgrown on porous NiSe₂ foam.

In some embodiments, the hybrid catalysts are also electrochemicallystable in 0.5M H₂SO₄. For example, after 1000 cycles, the polarizationcurve is almost the same as that of the initial one, indicating noobservable degradation after long-term cycling tests (FIG. 10c ). Thepractical operation of the catalyst was examined in electrolysis at afixed potential over a long period (FIG. 10d ), and at a givenoverpotential of −145 mV, there is no observable decrease in the currentdensity at ˜120 mA/cm² for electrolysis over 8 h for the hybridWS_(2(1-x))Se_(2x)/NiSe₂/NiSe₂ catalyst, indicating its potential usagein water splitting for a long time.

Further, in some embodiments to evaluate the differences in theelectrochemically effective surface areas of the catalysts disclosedherein, the electrochemical double-layer capacitances (Cdl) weremeasured via a simple cyclic voltammetry (CV) method as displayed inFIG. 11a,b . By drawing the current difference between anodic andcathodic current densities (Δj=j_(anodic)-j_(cathodic)) against eachscan rate at a given potential of 0.15 V, a linear fitting may beconducted, and the Cdl is derived from the linearly fitted curves, whichis half the value of the linear slopes. As shown in FIG. 11c , the Cdlvalues are extracted to be 256.9 mF/cm² for theWS_(2(1-x))Se_(2x)/NiSe₂/NiSe₂ hybrid catalyst, which is larger than180.9 mF/cm² of pure WS2/NiSe₂ foam and nearly 28.5 times of 9.0 mF/cm²of pure NiSe₂ foam. Thus, in some embodiments, given that there is alinear relationship between the electrochemical-surface area and thecapacitance Cdl, the relative electrochemically active surface area canbe derived, which may be further used to normalize the exchange currentdensity j_(0,normalized). In some embodiments the normalized exchangecurrent density of WS_(2(1-x))Se_(2x)/NiSe₂/NiSe₂ (8.54 μA/cm²) islarger than that of WS₂/NiSe₂ (6.46 μA/cm₂), suggesting improvedintrinsic catalytic activity by Se doping. Meanwhile, electrochemicalimpedance spectroscopy (EIS) was applied to study the electrode kineticsof the catalysts. Nyquist plots (FIG. 11d ) reveal a decrease ofcharge-transfer resistance (Rct) for the ternaryWS_(2(1-x))Se_(2x)/NiSe₂/NiSe₂ hybrid (0.8-1.3 Ω) in contrast to thebinary WS₂/NiSe₂ hybrid (3.2 Ω) and pure NiSe₂ foam (19.6 Ω).Furthermore, all of the catalysts exhibit very small series resistances(˜1 Ω), meaning that effective electrical integration is ensured bymetallic NiSe₂ foam.

In some embodiments, and on the basis of the improved catalyticperformance and EIS spectra, the substitution of S by Se atoms mayaffect the electrical conductivity of the ternary phaseWS_(2(1-x))Se_(2x)/NiSe₂ and thereby the hydrogen adsorption freeenergy. The enhanced electrical conductivity improves the electrontransfer between WS_(2(1-x))Se_(2x)/NiSe₂ catalyst and NiSe₂ support,and consequently, Cdl measurements and EIS results confirm thatWS_(2(1-x))Se_(2x)/NiSe₂/NiSe₂ hybrid catalyst exhibits more facileelectrode kinetics toward hydrogen evolution, which may be attributed tothe good conductivity and porous structures of the NiSe₂ foam, and theactive edge sites from WS_(2(1-x))Se_(2x)/NiSe₂ particles. Inconclusion, the catalytic HER activity of transition-metaldichalcogenides is increased by making 3D porous architectures oflayered WS_(2(1-x))Se_(2x)/NiSe₂ particles on metallic NiSe₂ foam. Goodconductivity and porous structures of NiSe₂ foam and a large number ofactive edge sites from WS_(2(1-x))Se_(2x)/NiSe₂ particles were created,which makes the hybrid catalyst highly active and efficient for HER, andstable in acid over a long period. Thus providing a basis for thefabrication of robust and stable electro-catalysts for large-scale watersplitting and satisfying an unmet need in the art. References citedherein are incorporated herein by this reference in their entirety).

While exemplary embodiments of the disclosure have been shown anddescribed, modifications thereof may be made by one skilled in the artwithout departing from the spirit and teachings of those embodiments.The embodiments described herein are exemplary only, and are notintended to be limiting. Many variations and modifications of thedisclosed embodiments are possible and are within the scope of theclaimed disclosure. Where numerical ranges or limitations are expresslystated, such express ranges or limitations should be understood toinclude iterative ranges or limitations of like magnitude falling withinthe expressly stated ranges or limitations (such as from about 1 toabout 10 includes, 2, 3, 4, etc.; greater than 0.10 includes 0.11, 0.12,0.13, etc.). For example, whenever a numerical range with a lower limit,R_(l), and an upper limit, R_(u), is disclosed, any number fallingwithin the range is specifically disclosed. In particular, the followingnumbers within the range are specifically disclosed: R=R_(l)+k*(R_(u)-R_(l)), wherein k is a variable ranging from 1 percent to 100percent with a 1 percent increment, i.e., k is 1 percent, 2 percent, 3percent, 4 percent, 5 percent, . . . 50 percent, 51 percent, 52 percent,95 percent, 96 percent, 97 percent, 98 percent, 99 percent, or 100percent. Moreover, any numerical range defined by two R numbers asdefined in the above is also specifically disclosed. Use of the term“optionally” with respect to any element of a claim is intended to meanthat the subject element is required, or alternatively, is not required.Both alternatives are intended to be within the scope of the claim. Useof broader terms such as comprises, includes, having, etc. should beunderstood to provide support for narrower terms such as consisting of,consisting essentially of, comprised substantially of, etc.

Accordingly, the scope of protection is not limited by the descriptionset out above but is only limited by the claims which follow, that scopeincluding all equivalents of the subject matter of the claims. Each andevery claim is incorporated into the specification as an embodiment ofthe present disclosure. Thus, the claims are a further description andare an addition to the embodiments of the present disclosure. Thedisclosures of all patents, patent applications, and publications citedherein are hereby incorporated by reference, to the extent that theyprovide exemplary, procedural or other details supplementary to thoseset forth herein.

1. A three dimensional (3D) hydrogen evolution reaction (HER) catalyst,comprising: a porous Ni foam support; a NiSe₂ scaffold positioned on thesupport; and a layered transition metal dichalcogenide (LTMDC)particles, or first-row transition metal dichalcogenides (TMDC)particles with binary or ternary phase positioned on the NiSe₂ scaffold.2. The catalyst of claim 1, wherein the layered transition metaldichalcogenides (LTMDC) particles are selected from the group consistingof CoS₂, CoSe₂, FeS₂, FeSe₂, NiSe₂, NiS₂, MoS₂, WS₂, MoSe₂, WSe₂, and acombination thereof.
 3. The catalyst of claim 1, wherein the layeredtransition metal dichalcogenides (LTMDC) particles compriseMoS_(2(1-x))Se_(2x) or WS_(2(1-x))Se_(2x) particles.
 4. The catalyst ofclaim 3, wherein the layered transition metal dichalcogenides (LTMDC)particles comprise vertically oriented layers or edge-oriented layers.5. The catalyst of claim 1, wherein the NiSe₂ scaffold comprisesmesoporous pores.
 6. The catalyst of claim 4, wherein the mesoporouspores are between 0.001 nm and 50 nm in diameter.
 7. The catalyst ofclaim 4, wherein the pores comprise a surface roughness (Ra) of between0.1 and
 50. 8. The catalyst of claim 4, wherein the NiSe₂ scaffoldcomprises active edge sites for HER.
 9. The catalyst of claim 1, whereinthe catalyst has at least one of: a low onset potential, large cathodecurrent density, small Tafel slopes, or large exchange current density.10. A method of making a three dimensional hydrogen evolution reaction(HER) catalyst, comprising: positioning a porous Ni foam support,selenizating said Ni foam support, and forming a NiSe₂ scaffold; andgrowing layered transition metal dichalcogenides (LTMDC) particles onthe NiSe₂ scaffold, to form a three dimensional hydrogen evolutionreaction (HER) catalyst.
 11. The method of claim 10, wherein saidselenizating is in an Ar atmosphere.
 12. The method of claim 10, whereinsaid selenizating is at 450° C.—600° C.
 13. The method of claim 10,wherein the NiSe₂ scaffold is HER active, and the grown layeredtransition metal dichalcogenides comprises a large number of exposedactive edge sites.
 14. The method of claim 10, wherein said layeredtransition metal dichalcogenide particles comprise MoS_(2(1-x))Se_(2x)particles or WS_(2(1-x))Se_(2x), particles.
 15. The method of claim 14,wherein said growing of said particles is in a vertical layerorientation from the NiSe₂ scaffold.
 16. The method of claim 15, whereinone layer of said particles is about 0.1 to 75 nm in thickness.
 17. Themethod of claim 10, wherein the layered transition metal dichalcogenides(LTMDC) particles are grown at between 450° C. and 600° C.
 18. Themethod of claim 10 wherein the catalyst comprises a large 3-D poroussurface area.
 19. An electrode, comprising: a three dimensional HydrogenEvolution Reaction (HER) catalyst, wherein said electrode comprises: aporous NiSe₂ foam support; and a layered transition metaldichalcogenides (LTMDC) particles, or first-row transition metaldichalcogenides positioned on the NiSe₂ scaffold, and wherein saidcatalyst has at least one of: a low onset potential, a large cathodecurrent density, a small Tafel slopes or a large exchange currentdensity.
 20. The electrode of claim 19, wherein a low onset potential isbetween −10 and 200 mV; a large cathode current density is between −10mV at 10 mA/cm² to about −120 mV at 10 mA/cm²; a small Tafel slopes isbetween 10 mV/dec to about 100 mV/dec; and a large exchange currentdensity is between 10 to about 1000 μA/cm².